Carbamates and their use as pesticides

ABSTRACT

O-Phenylcarbamates of the formula   AND PREPARATIONS CONTAINING THEM ARE BIOCIDES, E.G. INSECTICIDES.

United States Patent [191 Nikles et al. v

[ Dec. 24, 1974 CARBAMATES AND THEIR USE AS PESTICIDES [75] Inventors: Erwin Nikles, Allschwil; Volker Dittrich; Ladislaus Pinter, both of Basel, all of Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Nov. 15, 1971 [21] Appl. No.: 199,008

Related US. Application Data [60] Continuation of Ser. No. 758,616, Sept. 9, 1968, abandoned, which is a continuation-inpart of Ser. No. 647,274, April 28, 1967, abandoned, which is a division of Ser. No. 493,256, Oct. 5, 1965, abandoned.

[30] Foreign Application Priority Data Primary ExaminerAlbert T. Meyers Assistant ExaminerD. W. Robinson Attorney, Agent, or FirmFrederickl-I. Rabin [57] ABSTRACT O-Phenylcarbamates of the formula n o- CO--N/ 1 2 a 11 11 or alkyl R3, a nlkyl alkenyl, alkynyl 11 allcylunc or alkenyJcnn XIQ H, aliphatic radical, halogen 0! nitro X. (i or S and preparations containing them are biocides, e.g. insecticides.

12 Claims, No Drawings CARBAMATES AND THEIR USE AS PESTICIDES CROSS REFERENCES TO RELATED APPLICATIONS This is a continuation of application Ser. No. 758,616, filed Sept. 9, 1968, now abandoned. Said application is a continuation-in-part of application Ser. No. 647,274, filed Apr. 28, I967, now abandoned which in turn was a division of application Ser. No. 493,256, filed on Oct. 5, 1965, now abandoned.

SUMMARY OF THE INVENTION The present invention concerns and has for its object the provision of new O-phenyl-carbamates of Formula I in which each of R and R is hydrogen, lower alkyl or lower alkenyl, each of X and X is hydrogen, a saturated or unsaturated lower aliphatic radical, halogeno or nitro, X is oxygen or sulfur and each of R and R are alkyl, alkenyl or alkynyl or, when taken together, represent alkylene or alkenylene forming with the remaining moiety a 5 to 7 membered heterocycle, and in which R and R are unsubstituted or substituted by lower aliphatic radicals, halogeno, nitro or free or etherified hydroxy or mercapto, as well as of corresponding pesticidal preparations and methods for the preparation and application of these products. Said preparations are useful in the control of a wide variety of vegetable and animal pests.

DESCRIPTION OF THE PREFERRED EMBODIMENT The radicals R and R are identical or different and represent, for example, hydrogen, methyl, ethyl nor i-propyl or allyl.

The moiety in 0- or mposition results from reacting the corresponding aldehyde, semiacetal or semimercaptal, for example, with methanol, ethanol, propanol, isopropanol, allyl alcohol, propargyl alcohol, 2- methoxyethanol, 2-methylmercaptoethanol, 2- chlorethanol, Z-bromethanol or Z-hydroxyethanethiol, or the corresponding semiacetal with methylmercaptan, ethylmercaptan, n-propylmercaptan, isopropylmercaptan, n-butylmercaptan, allylmercaptan, chlorallylmercaptan, dichlorallylmercaptan, propargylmercaptan, 2-methoxyethanethiol, or Z-methylmercaptoethanethiol. In case R and R when taken together, represent alkylene or alkenylene, said moiety results from the reaction of the corresponding aldehyde, for example, with racemic l,2-propan-ediol, (+)(S)-l,2- propanediol, ()(R)-l,2-propanediol, 3-fluoro-l,2-

propanediol, 3-chloro-l,2-propanediol, 3-bromo-l,2- propanediol, 3-iodo-l,2-propanediol, 3-methoxy-l,2- propanediol, 3-ethoxy-1,2-propanediol, 3-isopropoxyl,2-propanediol, 3-allyloxy-l ,2-propanediol, 3-methallyloxyl ,2-propanediol, 3-propargyloxy-l ,2- propanediol, 3-acetoxy-l ,2-propanediol, 3- methylmercapto-l,2-propanediol, 3-chlorallylmercapto-l,2-propanediol, glycerol, l,3-propanediol, 2- chloro-l,3-propanediol, 2-bromo-l,3-propanediol, 2- nitro-1,3-propanediol, (+)(R)-l,2-butanediol, ()(S)- l,2-butanediol, racemic l,2-butanediol, 1,3- butanediol, 1,4-butanediol, meso-2,3-butanediol, (*)(2R:3R)-2,3-butanediol, (+)(2S:3S)-2,3- butanediol, l-butene-3,4-diol, 2-butene-l,4-diol, 2- hydroxymethyl-2-propen-l-ol, 2-hydroxymethyl-2- buten-l-ol, 2-methyl-l,2-propanediol, 3-chloro-2- methyl-l ,2-propanediol, 3-chloro-2-chloromethyl-l ,2- propanediol, Z-methyl-l,3-propanediol, methyl-l ,3-propanediol, l,2-pentanedio'l, l ,3- pentanediol, 2,3-pentanediol, 2,4-pentanediol, lpentene-3,4-diol, 2-methyl-l,2-butanediol, 2-methyl- 1,3-butanediol, 2-methyl-2,3-butanediol, 2-methyl-2,4- butanediol, 2-methyl-3,4-butanediol, 2-ethyl-l,3- propanediol, l,4-dichloro2-methyl-2,3-butanediol, 4- bromo-2-methyl-2,3-butanediol, 4-iodo-2-methyl-2,3- butanediol, 2,2-dimethyl-l ,3-propanediol, 2,2- bischloromethyl-l ,3-pr0panediol, 2,4-hexanediol, 2-methyl-2,3-pentanediol, 3-methyl-2,4-pentanediol, 2,2-dimethyl-3,4-butanediol, l,5-hexadiene-3,4-diol, 2-ethanol-l-thiol, 2-propanol-l-thiol, 3-chloro-2- propanoll-thiol, 3-propanol-l-thiol. Accordingly, each of R and R is preferably lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy-lower alkyl, lower alkylmercapto-lower alkyl, halo-lower alkyl, hydroxylower alkyl, halo-lower alkenyl, or R and R when taken together, preferably lower alkylene, monoor dihalo-lower alkylene, lower alkoxy-lower alkylene, lower alkenyloxy-lower alkylene, lower alkynyloxylower alkylene, lower alkanoyloxy-lower alkylene, lower alkylmercapto-lower alkylene, halo-lower alkenylmercapto-lower alkylene, hydroxy-lower alkylene, nitro-lower alkylene, lower alkenylene, hydroxylower alkenylene or lower alkadienylene. The term lower referred to above and hereinafter in connection with organic radicals or compounds respectively, defines such with up to 6 carbon atoms.

The radicals X, and X are identical or different and represent, for example, lower alkyl, e.g. methyl, lower alkoxy, alkenyloxy or alkynyloxy or -mercapto or haloalkenylmercapto, e.g., methoxy, isopropoxy, allyloxy, propargyloxy, methylmercapto, allylmercapto 0r chlorallylmercapto, halogeno, e.g. fluoro, chloro, bromo or iodo, trifluoromethyl, nitro, di-lower alkylamino or di-loweralkenylamino. Accordingly, the above mentioned aldehydes, represent, for example, salicylaldehyde, 4-methylsalicylaldehyde, S-methylsalicylaldehyde, 4-methoxy-salicylaldehyde, 4- isopropoxy-salicylaldehyde, 4-chloro-salicylaldehyde, 5-chloro-salicylaldehyde, S-bromo-salicylaldehyde, 5- methylmercapto-salicylaldehyde, 4-trifluoromethylsalicylaldehyde, S-nitro-salicylaldehyde, 4- dimethylamino-salicylaldehyde, 3 ,5-dichlorosalicylaldehyde, 3,5-dinitro-salicylaldehyde, 3- hydroxybenzaldehyde, 2-chloro-3- hydroxybenzaldehyde, 6-bromo-3- hydroxybenzaldehyde or 5-hydroxy-3- methylbenzaldehyde,

2-nitro-2- I The compounds of the invention exhibit valuable properties, for example, biocidal, especially insecticidal and acaricidal properties. Furthermore, they act also as herbicides, bactericides, fungicides and molluscicides. Inter alia, these carbamates develop a very strong action, for example, against houseflies, aphids, caterpillars and beetles, for example, corn weavil and Colorado beetle. Their contact effect is far superior to that of the known active substance Carbaryl (N- methyl-a-naphthylcarbamate).

They are not only suitable for use as herbicides, but when applied in a concentration that does not produce phytotoxic effects, they may also be used in plant protection since they develop an excellent effect against harmful microorganisms, for example against fungi, for example Alternaria solani, Phytopthora infestans and Septoria apii, as well as against harmful insects, acarides, nematodes and their ova and larvae. They may also be used quite generally as microbicides, for example, against Aspergillus species.

Particularly useful are compounds of Formula I in which each of R and R is hydrogen, lower alkyl or lower alkenyl, each of X and X is hydrogen, lower alkyl, lower alkoxy, lower alkenyloxy, lower alkynyloxy, lower alkylmercapto, lower alkenylmercapto, lower alkynylmercapto, lower haloalkenylmercapto, halogeno, trifluoromethyl, nitro, di-lower alkylamino or di-lower alkenylamino, X is oxygen or sulfur and each of R and R is lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy-lower alkyl, lower alkylmercapto-lower alkyl, halo-lower alkyl, hydroxy-lower alkyl, halo-lower alkenyl or R and R when taken together, represent lower alkylene, monoor di-halo-lower alkylene, lower alkoxy-lower alkylene, lower alkenyloxy-lower alkylene, lower alkynyloxy-lower alkylene, lower alkanoyloxylower alkylene, lower alkylmercapto-lower alkylene, halo-lower alkenylmercapto-lower alkylene, hydroxylower alkylene, nitro-lower alkylene, lower alkenylene, hydroxy-lower alkenylene or lower alkadienylene, forming with the remaining moiety a 5 to 7 membered heterocycle.

Especially suitable for insect control are the carbamates of Formula I wherein R is hydrogen, R is lower alkyl, each of X and X is hydrogen, methyl, chloro, bromo, trifluoromethyl or nitro, X is oxygen or sulfur and each of R and R is lower alkyl, lower alkenyl or lower alkynyl or R and R when taken together represent alkylene or alkenylene with 2 to 4 carbon atoms, forming with the remaining moiety a 5 to 7 membered heterocycle and being unsubstituted or substituted by halogen, nitro, hydroxy, lower alkoxy or lower alkenyloxy.

Preferred are compounds of Formulae H and Ill F-CO "'NllCll ()CO ""NHCH x. ...CH 5 j o--rt,, x n

CH and u II III in which X is oxygen or sulfur and each of R and R, is lower alkyl, lower alkenyl or lower alkynyl or R and R when taken together, represent alkylene or alkenylene with 2 to 4 carbon atoms, forming with the remaining moiety a to 7 membered heterocycle and being unsubstituted or substituted by halogen, nitro, hydroxy, lower alkoxy or lower alkenyloxy.

Most preferred are compounds of Formula lV O-C0 -NllCH 0 -CH"R in which X; is oxygen or sulfur and each of R and R is hydrogen, lower alkyl, lower alkenyl, halogen, hy droxy, lower alkoxy or lower alkenyloxy.

Outstanding are the compounds of Formula IV, in which X is oxygen or sulfur and each of R,-, and R is hydrogen or methyl.

The compounds of the invention are prepared, for

example, by reacting a phenol of the Formula V 3 3 x },Cll (V) O Rn with a reactive derivative of carbonic acid and with R NH-R The reaction of the phenol with the reactive derivative of carbonic acid and the amine may be carried out in either sequence, depending to some extent on the constitution of the required final product. Accordingly, said phenol or an alkali metal saltthereof may be reacted, for example, with phosgene and the resulting chlorocarbonate or carbonate condensed with R,N-

Alternatively, said amine may be first reacted with phosgene and the resulting carbamic acid chloride or (when R or R represents hydrogen) the isocyanate readily formed from it, may be reacted with the phenol. Furthermore, a urethane derived from the amine, preferably an alkyl urethane, may be reacted with the phenol (transesterification). It is also possible to react an urea derived from the amine with the phenol preferably at a raised temperature.

The products so obtained are open-chain or cyclic acetals ormercaptals, depending on the stoichiometric proportions of the starting materials and on the valency of the alcohols or mercaptans. According to the size of the ring and the kind of hetero atom present in the acetalized moiety, the carbamates of this invention may be designated as derivatives of l,3-dioxolan (from 1,2- glycols), of 1,3-dioxan (from 1,3-glycols), of 1,3- dioxan (from l,4-glycols) or of l,3-oxathiolans (from 1,2-hydroxymercaptans).

The starting materials used are known or, if new, can be prepared analogous to the method for the known products (cf. for example Houben-Weyl, Methoden der organischen Chemie, volume 7, part 1, Stuttgart 1945 For example, the phenols of Formula V are prepared by reacting an orthoor meta-hydroxy-benzaldehyde with a lower alcohol or mercaptan in the presence of an acid catalyst, for example zinc chloride, a mineral acid or paratoluenesulphonic acid. These reactions may also be carried out with aldehyde derivatives, for example oximes, aldehydanils or acetals (transacetalization). Another suitable route is the acetalization with the aid of the ortho-formic acid esters, formimine ethers, dimethylsulphite or ortho-silicic acid esters in the presence of lower aliphatic alcohols. Another route leading to said phenols is the reaction of suitable halides with alkali metal or alkaline earth metal alcoholates.

Said acetalization may be performed in two stages,

of a mixture of these two acids, or the sodium salt of a petroleumsulphonic acid. Suitable cationic dispersants are quaternary ammonium compounds, for example cetyl pyridinium bromide and dihydroxyethyl benzyl with the semiacetals or semimercaptals being formed in 5 dodecyl ammonium chloride.

the first reaction stage. When different alcohols are For the manufacture of dusting and casting preparaused in the two reaction stages, mixed acetals, i.e., tions, there may be used as solid vehicles:-talcum, kamonothioacetals, are obtained. olin, bentonite, calcium carbonate, calcium phosphate When optically active alcohols or mercaptans are or coal, cork meal, wood meal or other materials of used, there may be prepared optically active phenols of 10 vegtable origin. It is also very advantageous to manuthe Formula V and from them optically active carbafacture the preparations in the form of granulates. The mates of the Formula I. Ifits acetal moiety is cyclic and various forms of application may contain the convensubstituted, further isomerizing possibilities offer themtional additives that improve the distribution, the adheselves. A carbamate of the Formula I whose acetal resision, stability torain or the penetration; as such subdue is monosubstituted may be obtained in the cis-form l5 stances there may be mentioned fatty acids, resin, glue, or trans-form. in general, the present process for the casein and alginates. manufacture of said carbamates gives rise to mixtures The preparations of this invention may be used by of all possible isomers; these mixtures can be separated themselves or in conjunction or admixture with coninto their constituents by known methods, for x mple ventional pesticides, especially insecticides, acaricides, by crystallization. For the manufacture of the pr p r nematocides, bacteriocides, fungioides, herbioides and tions of this invention to be used for pest control, howthe ike. ever, the stereoisomer mixtures obtained in the manu- Th following Example are intended to illustrate the facture of the active substances are generall d, invention and are not to be construed as being limita- AS mentioned in the beginning the present invention tions thereon. Temperatures are given in degrees Cenalso provides pesticidal preparations comprising as the tigrade, and all parts or percentages wherever given are active ingredient at least one carbamate ofthe Formula Such y weight- I and, if desired, one of the following additives: Vehi- EXAMPLE I cles, solvents, diluents, dispersants, wetting agents, ad-

hesives, fertilizers and, if required, further pesticides. y 'P e Corresponding spray solutions are prepared, for exam- A mixture of 244 Parts efealleylaleehyde 125 Parts ple, with petroleum fractions having a high to medium of ethyleneglyeel 1 Part0f e ehlerlde l P y boiling range, for example Diesel oil or kerosene, coal of Concentrated P R F aeldiand 9 Pe y tar il or il f vegetabk or animal Origin, as we" as volume of benzene was boiled in a clrculatmg dist llahydrocarbons, for example alkylated naphthalenes, tetapparatus water was no longer bemg rahydronaphalene, if desired or required with the use nated- The 0f the pf e was filtefed and of xylene mixtures, cyclohexanols, ketones or chlorinaevaporated- The resldee was dlstllledounder hlgh Vile ted hydrocarbons for example trichloroethane or tetra- The P belled at 91 under 004 mm chloroethane, trichloroethylene or tri or tetrachloro- Hg Pressure and meltee at 67 to 70 C benzenes. It is advantageous to use organic solvents (H1041r3dloxolan'z'yl)'phenyl'N'methyl' having a boiling point above 100C. 40 carbamate It is especially advantageous to prepared aqueous A Solemn of Parts of ortho'(l3'dloxolanz'yn' forms of application from emulsion concentrates, Phenol 300 Pans by Volume of dry Yoluene w pastes or wenable Spray powders by addition of water mixed with about 0.2 part by volume of triethylam ne, Suitable emulsifiers or dispersants are non-ionic mod d 20 parts of methyhsocyanate were dropped ucts, for example condensation products of aliphatic 45 this solution at room temperature. The temperature alcohols, amines or carboxylic acids with a long-chain rose gradually to 31 The mlxture was kept for 1 day hydrocarbon residue or about 10 to 20 carbon atoms at temperature" The Product was miffed Offfnd with ethylene Oxide for example the Condensation crystallized from toluene; it melted at lll to H4 C.

roduct from octadecyl alcohol with 25 to 30 mols of e thylene oxide, or of commercial oleylamine with 15 5O EXAMPLE 2 mols of ethylene oxide, or of dodecylmercaptan with When glycols (polyols) were reacted with unsubstil2 mols of ethylene oxide. As suitable anionic emulsifituted or substituted orthoor metaers, there may be mentioned the following: The sodium hydroxybenzaldehydes, the condensation as described salt of dodecyl alcohol sulphuric acid ester, the sodium in Example I lead to cyclic acetals. When these acetals salt of dodecylbenzosulphonic acid, the potassium or were reacted with methyl-isocyanate, they furnished, triethanolamine salt of oleic acid or of abietic acid or for example, the following carbamates:

No. Aldehyde Glycol Cyclic acetal Carhamate l salicylaldehyde l,2-propanediol b.p.85C/0.03mm Hg ortho-(4-methyll.S-dioxolanQ-yll-phenyl-N- methyl-carbamate (crystallizes gradually) 2 do. 2,3-butanediol b.p.86C/().07mm Hg ortho-(4,5-dimethyl-l.3-dioxolan-2-yl)- phenyl N-methyl-carbamate, mp l()5C (commercial mixture of stereoisomers) 3 do. l-butene-3.4-diol b.p.82C/0.08mm Hg ortho-(4-vinyl-l.3-dioxolan-2 yll-phenyl-N- methyl-carbamate 4 do. glycerol-a-monob.p.l ll ll4C ortho-(4-chloromethyl-l.3-dioxolan-2-yl-)- plgscnyl-Nmethyl-carbamate. m.p. about 30 to chlorohydrin 0.3mm Hg Continued No. Aldehyde Glycol Cyclic acetal Carhamate do. glycerol m.p.148 to 149C ortho-(4-hydroxymethyl-l.3-dioxolan-2-yl)- phenyl-N-methyl-carbamate. or from acetonitrile ortho-(5-hydroxy-l.3-dioxan-2-yl)-phenyl-N- methyl-carbamate. m.p.l to 134C As hy-product the corresponding his-N-methylcarbamate melting at 170 to 172C was obtained.

6 do. 1,3-propanediol b.p92 to 96C ortho-( l.3-dioxan-2-yl)-phenyl-N-methylcarbamale. M.p.l25 to 127C (from toluene) 0.01mm Hg 7 do. 1,3-butanediol b.p.89 to 95C ortho-(4-methyl-l .3-dioxan-2-yl)-phenyl-N- methylcarbamate. M.p.l46 to 148C (from aeetonitrile) (106mm Hg 8 do. neopentylglycol b.p.90C/0.06mm ortho-(5,5-dimethyl-l.3-dioxan-2-yl)- henyl- N-methyl-carhamate. M.p.l22 to 124 C (from carbon tetrachloride) Hg m.p.58 C

9 salicylaldehyde 3-methyl-2,4- h.p.93C/0.01mm Hg ortho-(4.5.6-trimethy1-l.3-di0xan 2-yl)- phenyl-N-methyl-carhamate m.p. 118 to 136C pentandediol 10 do. 2-methyl-2-nitro-l,3- m.p.90 to 93C ortho-(5-methyl5-nitro-l .3 dioxan-2-y|)- phenyl-N-methyl-carhamate m.p.l3l 133C (from isopropanol) propanediol (from ether+ cyclohexane) 11 do. 2-butene-1,4- h.p.87C/0.03mm Hg ortho-( l,3-dioxep-5-en-2yl)-phenyl-N-methyl-carhamate m.p.94 C (from toluene) dio l2 4-methylsalicylethyleneglycol b.p.98C/0.02mm Hg; ortho-( l.3-dioxolan-2-yl)-meta'- methylphenyl-N-methyl-carbamate m.p.96 to 99C (from toluene) aldehyde crystallizes 13 5-methy1salicyldo. htp.95 96C ortho-(1,3-dioxolan-2-yl)-para-methylphenyl- N-methyl-carbamate m.p.l04 to 106C (from carbon tetrachloride) aldehyde 0.01mm Hg 14 mixture of 4- and 1.2-propanediol h.p.90C/0.7mm Hg ortho-(4-methyl-l,3-dioxolan-2-yl)-metaand meta'-trifluoromethylphcnyl-N-methyl carbamate (viscous oil) 6-trifluoromethyl-salicylaldehyde 15 S-chlorosalicylethyleneglycol m.p.82C (from para-chloro-ortho-( l.3-dioxolan-2-yl)-phenyl N-methyl carbamate m.p.l09 112C (from benzene+hexane) aldehyde toluene) l6 mixture of 4- and 1.2-propanediol b.p.93 98C/0.01mm Hg ortho-(4-methyl-1.3-dioxolan-2'yH-metaand meta-chlorophenyl-N-methyl carhamate. m.p. about 90 to 100C 6-chlorosalicylaldehyde 17 S-bromosalicylethyleneglycol m.p.8lC (from hexane) para-hromo-ortho-(1.3-dioxolan-2-yl) phenyl-H-methyl-carhamate, m.p. 107 to 109C (from ethylene chloride) aldehyde 18 3,5-dibromo-salicyldo. h.p.l45C/0.l7mm Hg ortho.para-dibromo-ortho-(1.3-dioxolan2- yl)-phenyl-N-methyl-carbamate m.p.l35 139C (from acetonitrilel aldehyde m.p.60 to 64C l9 3,5-dinitrodo. m.p. 134 140C (from ortho.para-dinitro-ortho'-(l.3-dioxolan-2-yl)- phenyl-N-ntethyl-carbamate m.p.149 C (from acetone) salicylaldehyde chlorobenzene) 20 meta-hydroxydo. b.p.l13 to 115C/0.03 meta-t1.3-dioxolan-2-yl)phenyl-N-mcthylcarbamate. m.p.73 to 77C (from toluene) benzaldehyde mm Hg 21 meta-hydroxy- 2.3-butanediol b.p.l l5C/0.lmm Hg meta-(4.5-dimethyl-1.3-dioxolan-2-yl) (commercial) phenyl-N-methyl-carbamate. viscous oil 4(6i-trifluoromethyl-salicylaldehyde can he prepared from 3-trifluommethy lphenol by the method of]. C. Duff [J.Chen1.Soc.19-ll. page 547. Prooluwn AcadtSCLSZ. page 191 (1945)]. ll hoils at 77 to 80C under 14mm Hg pressure.

Salicylaldehyde diethyl acetal A mixture of 122 parts of salicylaldehyde, parts of orthoformic acid ethyl ester and 120 parts of anhy- EXAMPLE 3 drous ethanol was mixed with 1 ml of concentrated hydrochcloric acid, whereupon the whole heated up spontaneously. After a short time, the solution was heated to the boil and then evaporated under vacuum. and the residue distilled under a high vacuum. The

product passed over at 80C under 0.15mm l-lg pressure. ortho-(diethoxymethyl)-phenyl-N-methyl-carbamate A solution of 138 parts of salicylaldehyde diethyl acetal, 46 parts of methylisocyanate and 0.5 part of triethylenediamine in 1,000 parts by volume of dry toleune was kept for 14 hours at room temperature. The resulting crystalline ortho-(diethoxymethyl)-phenyl-N- methyl-carbamate was filtered off, washed with 250 parts by volume of dry toluene and dried under vacuum. lt melted at 92 to 93C.

ortho-(Dimethoxymethyl)-phenyl-N-methylcarbamate, melting at 62 to 64C (after crystallization from dibutyl ether), was prepared in a similar manner, starting from salicylaldehyde dimethylacetal.

EXAMPLE 4 ortho-( 1,3-oxathiolan-2-yl )-phenol 82 Parts of 2-mercaptoethanol were mixed with 0.5 part by volume of concentrated hydrochloric acid then dropwise with 122 parts of salicylaldehyde; the temperature of the mixture rose. The reaction mixture was stirred for 1 hour at room temperature, then diluted with 500 parts by volume of ether and washed with sodium bicarbonate solution and then with water until the washings ran neutral. The solution was dried over anhydrous sodium sulphate, filtered and evaporated.

The viscous residue was heated under a high vacuum at a bath temperature of 160C, and the volatile phase was condensed. The condensate was then fractionated. At 112C under a pressure of 005mm Hg, the ortho- (l,3-oxathiolan-2-yl)-phenol formed passed over and crystallized on standing. It melted at 72 74C. ortho-( 1 ,3-oxathiolan-2-yl)-phenyl-N-methylcarbamate 15 Parts of methylisocyanate and 0.] part of triethylenediamine were added to a solution of 37 parts of ortho-(l,3-oxathiolan-2-yl)-phenol in 100 parts by volume of dry toluene. The mixture was moderately cooled to maintain its temperature below 35C. After a few hours, the resulting crystalline product was filtered off and recrystallized from toluene or carbon tetrachloride. lt melted at 108 to 109C.

EXAMPLE 5 ortho,para-dinitro-ortho'-( l,3-dioxo1an-2-yl)-phenol A mixture of 196 parts of 3,5-dinitrosalicylaldehyde, 70 parts of glycol and 500 parts by volume of benzene was boiled in the presence of 1 part of anhydrous zinc chloride and 1 part by volume of concentrated phosphoric acid in a circulation distillation apparatus, until water was no longer being eliminated. After cooling, the product were filtered off and crystallized from chlorobenzene; it melted at 134 to 140C. ortho,para-dinitro-ortho-( 1 ,3-dioxolan-2-yl)-phenyl- N,N-dimethyl-carbamate 11.3 Parts of dimethylcarbamic acid chloride were added to a mixture of 25.6 parts of ortho,para-dinitroortho'-(1,3-dioxolan-2-yl)-phenol, 200 parts by volume of chlorobenzene and 25 parts of triethylamine. The solution was heated for 5 hours at 130C, allowed to cool, filtered, washed with 2N-sodium carbonate solution and evaporated. The residue was crystallized from alcohol. The product melted at 141 to 142C.

, EXAMPLE 6 Dusting Agent Equal parts of an active substance described in Examples 1 to 5 were mixed with precipitated silica and finely ground. When this powder is mixed with kaolin or talcum, it may be used in the form of dusting preparations having the desired concentration of active substance. In general, preparations containing 1 to 5 percent of active substance are preferred.

Spray Powder To manufacture a spray powder, the following ingredients, for example, were mixed and then finely ground: 50 parts of an active substance of Examples 1 to 5 20 parts of Hisil (highly adsorbent, precipitated silica) 25 parts of bolus alba (kaolin) 3.5 parts of a reaction product from para-tertiary octylphenol and ethylene oxide 1.5 parts of sodium l-benzyl-2-stearyl-benzimidazole- 6,3-disulphonate.

Emulsion Concentrate Readily soluble active substances were also formulated in the form of an emulsion concentrate as follows: 20 parts of active substance parts of xylene 10 parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecyl benzene-sulphonate were mixed. On dilution with water to the desired concentration, an emulsion suitable for spraying was obtained.

EXAMPLE 7 The active substance of Example 1 and the active substance Carbaryl were subjected to a comparative test to establish their contact effect against houseflies and corn weavils. The new substance displayed a much greater, distinct contact-insecticidal effect.

When applied in a concentration of 0.04 percent in the control of aphide (aphis fabae) on young bean plants, it was found that after 2 days the active substance of Example 1 had completely destroyed the aphids. It was found to have a good diffusion and distinct systemic effect.

Carbaryl was found to be ineffective in these tests. Carbaryl has the composition of l-naphthyl-N-methylcarbamate.

The above-mentioned active substance is active in limit concentrations of 1.2 parts per million against aedes larvae (24 hours).

The compound was also tested in dust form against various pests (1 percent, Zg/m 20kg per hectare) and the following results were recorded:

after after 6 hours 24 hours Periplaneta arnericana Phyllodronia germanica 100% Porcellic seaber 100% Formica rufa 100% Phosphoric acid ester 1 6 do. 111 9 active substance of in 7 per pest -Continued Example I 2 0,0-dimethyl 3-methyl-4-nitrophenyl l-thionophosphate ll 0,0-dimethyl-O-( Lchloro-l -N-dielhyl-carbaminyl-l-propen- 2-yl)-phosphate lll OD-dimethyl-O-t 4-methylmercapto-B-methyl-phenyl thinophosphate.

wherein each of R and R is hydrogen or lower alkyl and X is oxygen or sulfur, and (2) a suitable carrier.

2. A preparation according to claim 1 in which the compound is o-( l ,3-dioxolan-2-yl)-phenyl-N- methylcarbamate.

3. A method for controlling insects which comprises applying thereto an insecticidally effective amount of a compound of the formula wherein X, is oxygen or sulfur and each of R and R is hydrogen or lower alkyl.

4. A method according to claim 1 in which, in the compound, each of R and R is hydrogen or methyl.

5. The method of claim 4 in which the compound is o-( l,3-dioxolan-2-yl)-phenyl-N-methylcarbamate.

6. The method according to claim 4 in which the compound is o-(4-methyll ,3-dioxolan-2-yl )-phenyl-N- methylcarbamate.

7. The method according to claim 4 in which the compound is o-(4,5-dimethyl-l,3-dioxolan-2-yl)- phenyl-N-methylcarhamate.

8. The method according to claim 4 in which the compound is o-( l ,3-oxathiolan-2-yl )-phenyl-N- methylcarbamate.

9. A method for controlling insects which comprises applying thereto an insecticidally effective amount of o-( l ,3-di0xan-2-yl)-phenyl-Nmethylcarbamate.

10. A method for controlling insects which comprises applying thereto an insecticidally effective amount of o-( l ,3-dioxep-5-en-2-yl )-phenyl-N-methylcarbamate.

11. A method for treating living plants infected by bacteria which comprises applying to said plants a bactericidally effective amount of a compound of the formula O-CO-NHCH O -CO-NHCH X CHR 3 5 CH l O- CH-R in which each of R and R is hydrogen or lower alkyl 

1. A PREPARATION FOR COMBATTING INSECTS COMPRISING (1) AS ACTIVE INGREDIENT AN INSECTICIDALLY EFFECTIVE AMOUNT OF AN 0-PHENYL CARBAMATE COMPOUND OF THE FORMULA
 2. A preparation according to claim 1 in which the compound is o-(1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate.
 3. A method for controlling insects which comprises applying thereto an insecticidally effective amount of a compound of the formula
 4. A method according to claim 1 in which, in the compound, each of R5 and R6 is hydrogen or methyl.
 5. The method of claim 4 in which the compound is o-(1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate.
 6. The method according to claim 4 in which the compound is o-(4-methyl-1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate.
 7. The method according to claim 4 in which the compound is o-(4,5-dimethyl-1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate.
 8. The method according to claim 4 in which the compound is o-(1,3-oxathiolan-2-yl)-phenyl-N-methylcarbamate.
 9. A method for controlling insects which comprises applying thereto an insecticidally effective amount of o-(1,3-dioxan-2-yl)-phenyl-N-methylcarbamate.
 10. A method for controlling insects which comprises applying thereto an insecticidally effective amount of o-(1,3-dioxep-5-en-2-yl)-phenyl-N-methylcarbamate.
 11. A method for treating living plants infected by bacteria which comprises applying to said plants a bactericidally effective amount of a compound of the formula
 12. A method for treating plants infested by phyto-pathogenic fungi, which comprises applying to said plants a fungicidally effective amount of a compound of the formula 